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Elucidating Anomalous Intensity Ratios in Chlorine L-Edge X-ray Absorption Spectroscopy: Multiplet Effects and Core
Zhe Lin1, Junzi Liu1, Chaoqun Zhang1
1Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States.
Abstract:
A relativistic core-valence-separated equation-of-motion coupled cluster (CVS-EOM-CC) study of chlorine L2,3-edge X-ray absorption near-edge structure (XANES) spectra using CH3Cl and CH2ICl as representative molecules is reported. The nearly identical intensity for the main features in the L2- and L3-edge XANES spectra is attributed to multiplet effects and the overlap between core-valence and core Rydberg transitions. The multiplet effects originating from the interaction between the core hole and the C-Cl σ* orbitals account for around half of the deviation of the L3 and L2 intensity ratio from the 2:1 ratio of the numbers of 2p3/2 and 2p1/2 electrons. The 2p3/2 → 4s core Rydberg transitions are shown to overlap with the 2p1/2 → σ* transitions and contribute to the other half of the intensity anomaly. We demonstrate that triple excitations in CVS-EOM-CC calculations play important roles in accurate simulation of the overlap between the 2p1/2 → σ* and 2p3/2 → 4s transitions.
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